U.S. patent application number 11/289448 was filed with the patent office on 2006-04-13 for rtv heat conductive silicone rubber compositions.
This patent application is currently assigned to Shin-Etsu Chemical Co., Ltd.. Invention is credited to Jun Horikoshi, Tsuneo Kimura, Kei Miyoshi.
Application Number | 20060079634 11/289448 |
Document ID | / |
Family ID | 36146225 |
Filed Date | 2006-04-13 |
United States Patent
Application |
20060079634 |
Kind Code |
A1 |
Horikoshi; Jun ; et
al. |
April 13, 2006 |
RTV heat conductive silicone rubber compositions
Abstract
A RTV heat conductive silicone rubber composition comprising (A)
an organopolysiloxane having hydrolyzable groups at both ends, (B)
an organopolysiloxane having at least one hydrolyzable group at one
end, (C) a heat conductive filler, and (D) an organosilicon
compound having a hydrolyzable group or a partial hydrolytic
condensate thereof experiences a minimized viscosity increase even
when loaded with a large amount of heat conductive filler (C), has
good potting, coating and sealing properties, and is suited for use
in one package form.
Inventors: |
Horikoshi; Jun; (Gunma-ken,
JP) ; Kimura; Tsuneo; (Gunma-ken, JP) ;
Miyoshi; Kei; (Gunma-ken, JP) |
Correspondence
Address: |
BIRCH STEWART KOLASCH & BIRCH
PO BOX 747
FALLS CHURCH
VA
22040-0747
US
|
Assignee: |
Shin-Etsu Chemical Co.,
Ltd.
|
Family ID: |
36146225 |
Appl. No.: |
11/289448 |
Filed: |
November 30, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10854278 |
May 27, 2004 |
|
|
|
11289448 |
Nov 30, 2005 |
|
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Current U.S.
Class: |
524/588 |
Current CPC
Class: |
C08G 77/045 20130101;
C08L 83/14 20130101; C08L 83/14 20130101; C08L 2666/54 20130101;
C08L 83/00 20130101; C08L 2666/54 20130101; C08L 83/00 20130101;
C08L 83/00 20130101; H01L 23/3737 20130101; C08G 77/18 20130101;
C08L 83/14 20130101; C08L 83/04 20130101; H01L 2924/0002 20130101;
H01L 2924/00 20130101; C08L 83/00 20130101; C08L 2666/44 20130101;
C08L 2666/44 20130101; C08G 77/70 20130101; C08G 77/16 20130101;
C08L 83/04 20130101; C08L 83/04 20130101; H01L 2924/0002 20130101;
C08G 77/20 20130101 |
Class at
Publication: |
524/588 |
International
Class: |
C08L 83/04 20060101
C08L083/04; C08L 83/00 20060101 C08L083/00 |
Foreign Application Data
Date |
Code |
Application Number |
May 30, 2003 |
JP |
2003-155286 |
May 27, 2004 |
DE |
102004025867.8 |
May 28, 2004 |
CN |
200410055033.2 |
Claims
1. A RTV heat conductive silicone rubber composition comprising (A)
60 to 99% by weight of an organopolysiloxane of the general formula
(1): ##STR9## wherein R.sup.1 is hydrogen or a substituted or
unsubstituted monovalent hydrocarbon group, R.sup.2 is a
substituted or unsubstituted monovalent hydrocarbon group, Z is an
oxygen atom or a divalent hydrocarbon group, a is 0, 1 or 2, and n
is an integer of at least 10, (B) 1 to 40% by weight of a
hydrolyzable group-containing organopolysiloxane of the general
formula (2): ##STR10## wherein R.sup.3 is a substituted or
unsubstituted monovalent hydrocarbon group, R.sup.4 is a
substituted or unsubstituted monovalent hydrocarbon group, b is 0,
1 or 2, and m is an integer of 5 to 90, the sum of components (A)
and (B) being 100% by weight, (C) 100 to 4,000 parts by weight of a
heat conductive filler per 100 parts by weight of components (A)
and (B) combined, and (D) 1 to 50 parts by weight of an
organosilicon compound per 100 parts by weight of components (A)
and (B) combined, the organosilicon compound having the formula:
R.sup.5.sub.cSiX.sub.4-c wherein R.sup.5 is a substituted or
unsubstituted monovalent hydrocarbon group, X is a hydrolyzable
group, and c is 0, 1 or 2, or a partial hydrolytic condensate
thereof.
2. The composition of claim 1, wherein R.sup.3 in formula (2) is
methyl group, vinyl group or phenyl group, and R.sup.4 in formula
(2) is methyl group or ethyl group.
3. The composition of claim 1, wherein the heat conductive filler
(C) comprises at least one member selected from the group
consisting of inorganic powders such as aluminum oxide, zinc oxide,
ground quartz, silicon carbide, silicon nitride, magnesium oxide,
aluminum nitride, boron nitride and graphite, and metal powders
such as aluminum, copper, silver, nickel, iron and stainless
steel.
4. The composition of claim 3, wherein the heat conductive filler
(C) comprises at least one member selected from the group
consisting of aluminum oxide, aluminum nitride and boron
nitride.
5. The composition of claim 1, which is of one package type.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation-in-part of copending
application Ser. No. 10/854,278 filed on May 27, 2004, the entire
contents of which are hereby incorporated by reference.
TECHNICAL FIELD
[0002] This invention relates to room temperature vulcanizable
(RTV) has a high stability, heat conductive silicone rubber
compositions which undergo only a little viscosity buildup when
loaded with large amounts of heat conductive fillers, have good
potting, coating and sealing properties, and are suited for use in
one package form.
BACKGROUND OF THE INVENTION
[0003] Heat-generating parts such as power transistors and
thyristors deteriorate their performance due to the heat generated.
It is a common practice in the prior art that such heat-generating
parts are provided with heat sinks for heat dissipation or suitable
means for conducting heat to a metal chassis of the associated
equipment for heat release. To improve both electrical insulation
and heat transfer, heat-dissipating, electrically insulating sheets
of silicone rubber loaded with heat conductive fillers often
intervene between heat-generating parts and heat sinks.
[0004] As the heat-dissipating, electrically insulating material,
JP-A 47-32400 discloses an electrically insulating composition
comprising 100 parts by weight of synthetic rubber, typically
silicone rubber and 100 to 800 parts by weight of at least one
metal oxide selected from beryllium oxide, aluminum oxide, hydrated
aluminum oxide, magnesium oxide, and zinc oxide.
[0005] As the heat-dissipating material for use in areas where
electrical insulation is not required, JP-A 56-100849 discloses an
addition curing type silicone rubber composition comprising 100
parts by weight of a silicone rubber and 60 to 500 parts by weight
of silica and a heat conductive powder such as silver, gold or
silicon.
[0006] These heat conductive materials, however, are very difficult
to mold and work in that the liquid silicone rubber compositions
lose fluidity if loaded with large amounts of heat conductive
fillers in order to improve the heat transfer.
[0007] Then U.S. Pat. No. 6,306,957 proposes a heat conductive
silicone rubber composition which undergoes only a little viscosity
buildup when loaded with large amounts of heat conductive fillers.
This composition is of thermosetting type. No reference is made
therein to the RTV type.
[0008] In electronic machines such as personal computers and CD-ROM
drives, IC chips including LSI and CPU are increased in the degree
of integration. Since such closely integrated IC chips generate
more amounts of heat, conventional cooling means including heat
sinks and cooling fans are sometimes unsatisfactory. In particular,
lap-top personal computers are difficult to built in large heat
sinks or cooling fans because only a limited space is available
inside. In such machines, IC chips are mounted on printed circuit
boards which use as the substrate glass-reinforced epoxy resins and
polyimide resins characterized by poor heat conduction. It is then
ineffective to release heat to the substrates through
heat-dissipating, electrically insulating sheets as in the prior
art.
[0009] Then, heat-dissipating parts of air cooling or forced
cooling type are disposed in proximity to IC chips so that the heat
generated in the chips is conducted to the heat-dissipating parts.
When the heat-dissipating part is in close contact with the IC
chip, heat transfer is retarded due to surface irregularities. When
a heat-dissipating, electrically insulating sheet intervenes
between the heat-dissipating part and the IC chip, the less
flexibility of the insulating sheet allows the differential thermal
expansion between the chip and the part to apply stresses to the
chip, posing a possibility of chip failure. Additionally, the
attachment of a heat-dissipating part to each circuit chip requires
an extra space, preventing size reduction. A system capable of
cooling a plurality of IC chips with a single heat-dissipating part
is employed in such cases. In particular, CPU's of the TCP type
used in lap-top personal computers require deliberate consideration
of a cooling system because they have a reduced height, but an
increased heat release as compared with ordinary CPU's.
[0010] Where semiconductor chips of different heights are arranged
with gaps therebetween, a liquid silicone rubber composition
capable of filling the varying gaps becomes necessary. As the drive
frequency becomes higher, CPU's are developed which have improved
performance, but produce larger amounts of heat. A better heat
conductive material is desired in this regard too.
[0011] An attempt to load a heat conductive liquid silicone rubber
composition with a large amount of heat conductive filler for
enhancing its heat conductivity results in a composition which
loses fluidity and becomes awkward to work.
[0012] In the case of addition cure (thermosetting) silicone rubber
compositions, a heating means is necessary for curing. A
consideration of the heat resistance of IC chips prohibits heating
to high temperatures of 60.degree. C. or higher. Additionally, the
use of heating means suggests an extra capital investment.
SUMMARY OF THE INVENTION
[0013] Therefore, an object of the invention is to provide a RTV
heat conductive silicone rubber composition which has a high
stability even after a long-term storage in a cartridge, is
minimized in viscosity increase even when loaded with a large
amount of heat conductive filler, has good potting, coating and
sealing properties, and is suited for use in one package form.
[0014] The inventors have found that blending components (A) and
(B) to be defined below results in a RTV heat conductive silicone
rubber composition which undergoes only a little viscosity buildup
when loaded with a large amount of heat conductive filler, and
maintains good potting, coating and sealing properties. The
composition is best suited as a heat dissipating material.
[0015] Especially, the RTV heat conductive rubber composition
containing components (A) and (B) and a large amount of heat
conductive filler is cured by moisture when exposed in the air. It
is necessary to store such a composition in a cartridge or
container in the sealed state so that the composition is not
exposed in the air or moisture and thus is not cured upon
storage.
[0016] The RTV heat conductive rubber composition has a high
stability even after a long-term storage without separating the
heat conductive filler from components (A) and (B) in a cartridge
or container.
[0017] The composition is used as it is in the state that the
composition is taken out from the cartridge or container. Even if
the filler is separated from components (A) and (B) in the
composition, it is practically impossible to disperse the filler in
the polymer again by mixing since the composition starts curing
immediately after it is exposed in the air or moisture.
[0018] When component (B) is incorporated in the specific amount,
the filler is not separated nor deposited in the composition with
only a little viscosity buildup when loaded with large amounts of
heat conductive filler.
[0019] The present invention provides a room temperature
vulcanizable (RTV) heat conductive silicone rubber composition
comprising
[0020] (A) 60 to 99% by weight of an organopolysiloxane of the
general formula (1): ##STR1## wherein R.sup.1 is hydrogen or a
substituted or unsubstituted monovalent hydrocarbon group, R.sup.2
is a substituted or unsubstituted monovalent hydrocarbon group, Z
is an oxygen atom or a divalent hydrocarbon group, a is 0, 1 or 2,
and n is an integer of at least 10,
[0021] (B) 1 to 40% by weight of a hydrolyzable group-containing
organopolysiloxane of the general formula (2): ##STR2## wherein
R.sup.3 is a substituted or unsubstituted monovalent hydrocarbon
group, R.sup.4 is a substituted or unsubstituted monovalent
hydrocarbon group, b is 0, 1 or 2, and m is an integer of 5 to 90,
the sum of components (A) and (B) being 100% by weight,
[0022] (C) 100 to 4,000 parts by weight of a heat conductive filler
per 100 parts by weight of components (A) and (B) combined, and
[0023] (D) 1 to 50 parts by weight of an organosilicon compound per
100 parts by weight of components (A) and (B) combined, the
organosilicon compound having the formula: R.sup.5.sub.cSiX.sub.4-c
wherein R.sup.5 is a substituted or unsubstituted monovalent
hydrocarbon group, X is a hydrolyzable group, and c is 0, 1 or 2,
or a partial hydrolytic condensate thereof.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Component A
[0024] In the RTV heat conductive silicone rubber composition of
the invention, component (A) serving as the base is an
organopolysiloxane of the following general formula (1). ##STR3##
Herein R.sup.1 is hydrogen or a substituted or unsubstituted
monovalent hydrocarbon group, R.sup.2 is a substituted or
unsubstituted monovalent hydrocarbon group, Z is an oxygen atom or
a divalent hydrocarbon group, a is 0, 1 or 2, and n is an integer
of at least 10.
[0025] More particularly, R.sup.1 is preferably selected from among
hydrogen and substituted or unsubstituted monovalent hydrocarbon
groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms,
for example, alkyl groups such as methyl, ethyl and propyl,
halogenated hydrocarbon groups such as chloromethyl,
trichloropropyl and trifluoropropyl, cyano-hydrocarbon groups such
as 2-cyanoethyl, 3-cyanopropyl and 2-cyanobutyl, vinyl, allyl,
isopropenyl, and phenyl. In the event a=0 or 1, monovalent
hydrocarbon groups are preferred, with methyl and ethyl being
especially preferred. In the event a=2, hydrogen is preferred.
[0026] R.sup.2 is preferably selected from among substituted or
unsubstituted monovalent hydrocarbon groups having 1 to 15 carbon
atoms, preferably 1 to 10 carbon atoms, for example, alkyl groups
such as methyl, ethyl, propyl, isopropyl, butyl, 2-ethylbutyl and
octyl, cycloalkyl groups such as cyclohexyl and cyclopentyl,
alkenyl groups such as vinyl and allyl, aryl groups such as phenyl,
tolyl, xylyl, naphthyl, biphenylyl and phenanthryl, aralkyl groups
such as benzyl and phenylethyl, halogenated hydrocarbon groups such
as chloromethyl, trichloropropyl, trifluoropropyl, bromophenyl and
chlorocyclohexyl, and cyano-hydrocarbon groups such as
2-cyanoethyl, 3-cyanopropyl and 2-cyanobutyl. Of these, methyl,
vinyl, phenyl and trifluoropropyl are preferred, with methyl being
especially preferred.
[0027] Z is typically an oxygen atom or an alkylene group having 1
to 12 carbon atoms, preferably 1 to 10 carbon atoms such as
methylene, ethylene or propylene. Of these, oxygen and ethylene are
preferred.
[0028] In formula (1), n is an integer of at least 10 such that the
organopolysiloxane may have a viscosity at 23.degree. C. of at
least 25 mPas, preferably 100 to 1,000,000 mPas, more preferably
500 to 200,000 mPas.
Component B
[0029] Component (B) is a diorganopolysiloxane having a
hydrolyzable group, represented by the general formula (2).
##STR4## Herein R.sup.3 is a substituted or unsubstituted
monovalent hydrocarbon group, R.sup.4 is hydrogen or a substituted
or unsubstituted monovalent hydrocarbon group, b is 0, 1 or 2, and
m is an integer of 5 to 90.
[0030] More particularly, R.sup.3 is preferably selected from among
unsubstituted monovalent hydrocarbon groups having 1 to 15 carbon
atoms, especially 1 to 10 carbon atoms and substituted forms of the
foregoing groups in which some hydrogen atoms are substituted with
halogen atoms or the like. R.sup.3 groups may be the same or
different. Examples of R.sup.3 include alkyl groups such as methyl,
ethyl, propyl, isopropyl, butyl, 2-ethylbutyl and octyl, cycloalkyl
groups such as cyclohexyl and cyclopentyl, alkenyl groups such as
vinyl and allyl, aryl groups such as phenyl, tolyl, xylyl,
naphthyl, biphenylyl and phenanthryl, aralkyl groups such as benzyl
and phenylethyl, halogenated hydrocarbon groups such as
chloromethyl, trichloropropyl, trifluoropropyl, bromophenyl and
chlorocyclohexyl, and cyano-hydrocarbon groups such as
2-cyanoethyl, 3-cyanopropyl and 2-cyanobutyl. Of these, methyl,
vinyl and phenyl are preferred, with methyl being especially
preferred.
[0031] R.sup.4 is preferably selected from among hydrogen and
substituted or unsubstituted monovalent hydrocarbon groups having 1
to 6 carbon atoms, preferably 1 to 4 carbon atoms, for example,
alkyl groups such as methyl, ethyl and propyl, halogenated
hydrocarbon groups such as chloromethyl, trichloropropyl and
trifluoropropyl, cyano-hydrocarbon groups such as 2-cyanoethyl,
3-cyanopropyl and 2-cyanobutyl, vinyl, allyl, isopropenyl, and
phenyl. Of these, methyl and ethyl are preferred, with methyl being
most preferred.
[0032] The subscript b is 0, 1 or 2, preferably 0 or 1, and most
preferably 0. The molecule of component (B) is terminated with at
least one hydrolyzable group.
[0033] In formula (2), m is an integer of 5 to 90, preferably 10 to
80, more preferably 20 to 60, most preferably 25 to 40, especially
28 to 35. If m is outside the range, the diorganopolysiloxane
becomes less effective for reducing the viscosity of the
composition and the stability of the resulting composition becomes
inferior.
[0034] Component (B) is incorporated in an amount of 1 to 40% by
weight, preferably 2 to 35% by weight, more preferably 5 to 30% by
weight of the total weight of components (A) and (B). A small
amount of component (B) is less effective for reducing the
viscosity of the composition. If component (B) or hydrolyzable
group-containing organopolysiloxane is used in a large amount, the
heat conductive filler settles down with the passage of time or the
organopolysiloxane bleeds out after curing.
[0035] Typical examples of component (B) or hydrolyzable
group-containing organopolysiloxane are given below although it is
not limited thereto. ##STR5## Component C
[0036] Component (C) is a heat conductive filler. Use may be made
of at least one inorganic powder selected from among aluminum
oxide, zinc oxide, ground quartz, silicon carbide, silicon nitride,
magnesium oxide, aluminum nitride, boron nitride and graphite, or
at least one metal powder selected from among aluminum, copper,
silver, nickel, iron and stainless steel. A combination of any of
these powders is useful. Aluminum oxide, aluminum nitride and boron
nitride are preferred.
[0037] With respect to the blending proportion of the
organopolysiloxanes as components (A) and (B) and the filler as
component (C), 100 to 4,000 parts by weight, preferably 250 to
3,000 parts by weight of component (C) is used per 100 parts by
weight of components (A) and (B) combined. Less amounts of
component (C) endow the composition with insufficient heat
conductivity. Larger amounts of component (C) are difficult to
blend and increase the viscosity of the composition to a level to
impede working.
[0038] The heat conductive filler preferably has a mean particle
size of up to 50 .mu.m, more preferably 0.1 to 40 .mu.m and most
preferably 0.2 to 30 .mu.m. A filler with a mean particle size in
excess of 50 .mu.m is less dispersible so that when a silicone
rubber liquid loaded therewith is allowed to stand, the filler will
settle out. The heat conductive filler is preferably of a round
shape approximate to a sphere. A filler of rounder shape is more
effective for preventing a viscosity rise even at high loadings.
Such spherical heat conductive fillers are commercially available
under the trade name of spherical alumina AS series from Showa
Denko K.K. and high purity spherical alumina AO series from
Admatechs K.K. In the practice of the invention, it is recommended
to combine a heat conductive filler powder fraction having a large
mean particle size and a heat conductive filler powder fraction
having a small mean particle size in a ratio corresponding to the
theoretical closest packing distribution curve. This improves the
packing efficiency, achieving a lower viscosity and a higher
thermal conductivity. Specifically, a heat conductive filler powder
fraction having a mean particle size of less than 5 .mu.m,
preferably 0.1 to 3 .mu.m is combined with a heat conductive filler
powder fraction having a mean particle size of at least 5 .mu.m,
preferably 5 to 40 .mu.m. Their proportion is preferably between
10:90 and 90:10, more preferably between 20:80 and 80:20 in weight
ratio.
Component D
[0039] The curing agent used herein is a silane having at least two
hydrolyzable groups in a molecule, represented by the formula:
R.sup.5.sub.cSiX.sub.4-c wherein R.sup.5 is a substituted or
unsubstituted monovalent hydrocarbon group, X is a hydrolyzable
group, and c is 0, 1 or 2, or a partial hydrolytic condensate
thereof. More particularly, R.sup.5 is a substituted or
unsubstituted monovalent hydrocarbon group preferably having 1 to
10 carbon atoms, more preferably 1 to 8 carbon atoms, such as
methyl, ethyl, propyl, vinyl or phenyl. Suitable hydrolyzable
groups represented by X include alkoxy groups such as methoxy,
ethoxy and butoxy, ketoxime groups such as dimethylketoxime and
methylethylketoxime, acyloxy groups such as acetoxy, alkenyloxy
groups such as isopropenyloxy and isobutenyloxy, amino groups such
as N-butylamino and N,N-diethylamino, and amide groups such as
N-methylacetamide.
[0040] The curing agent is used in an amount of 1 to 50 parts by
weight per 100 parts by weight of components (A) and (B) combined,
i.e., both end hydroxyl or organooxy group-capped
organopolysiloxane plus one end hydroxyl or organooxy group-capped
organopolysiloxane. Less than 1 part by weight of the curing agent
fails to achieve sufficient crosslinking or to produce a
composition having desired rubbery elasticity. A composition with
more than 50 parts by weight of the curing agent exhibits an
increased shrinkage factor upon curing and poor mechanical
properties. Preferably the curing agent is used in an amount of 3
to 20 parts by weight.
Curing Catalyst
[0041] The silicone rubber composition of the invention is of
condensation curing type wherein a curing catalyst is often used.
Suitable curing catalysts include alkyltin esters such as
dibutyltin diacetate, dibutyltin dilaurate and dibutyltin
dioctoate; titanic acid esters or titanium chelate compounds such
as tetraisopropoxytitanium, tetra-n-butoxytitanium,
tetrakis(2-ethylhexoxy)titanium,
dipropoxybis(acetylacetonato)titanium, and titanium
isopropoxyoctylene glycol; organometallic compounds such as zinc
naphthenate, zinc stearate, zinc 2-ethyloctoate, iron
2-ethylhexoate, cobalt 2-ethylhexoate, manganese 2-ethylhexoate,
cobalt naphthenate, and alkoxyaluminum compounds;
amonoalkyl-substituted alkoxysilanes such as
3-aminopropyltriethoxysilane and
N-.beta.-(aminoethyl)-.gamma.-aminopropyltrimethoxysilane; amine
compounds and salts thereof such as hexylamine and dodecylamine
phosphate; quaternary ammonium salts such as benzyltriethylammonium
acetate; alkali metal salts of lower fatty acids such as potassium
acetate, sodium acetate and lithium oxalate; dialkylhydroxylamines
such as dimethylhydroxylamine and diethylhydroxylamine; and silanes
or siloxanes containing a guanidyl group such as
tetramethylguanidylpropyltrimethoxysilane,
tetramethylguanidylpropylmethyldimethoxysilane, and
tetramethylguanidylpropyltris(trimethylsiloxy)silane, alone or in
admixture of any. The curing catalyst is used in an amount of 0 to
10 parts by weight, preferably 0.01 to 5 parts by weight per 100
parts by weight of components (A) and (B) combined.
Filler
[0042] In the RTV heat conductive silicone rubber composition of
the invention, various other fillers may be compounded, if
necessary. Suitable fillers include fumed silica, precipitated
silica, diatomaceous earth, metal oxides such as iron oxide and
titanium oxide, metal carbonates such as calcium carbonate,
magnesium carbonate and zinc carbonate, asbestos, glass wool,
carbon black, finely divided mica, fused silica powder, and
powdered synthetic resins such as polystyrene, polyvinyl chloride,
and polypropylene. The fillers may be compounded in any desired
amount as long as the objects of the invention are not impaired.
Preferably, the filler has been removed of water by pre-drying,
prior to use. In the RTV heat conductive silicone rubber
composition of the invention, pigments, dyes, anti-aging agents,
antioxidants, antistatic agents, and flame retardants such as
antimony oxide and chlorinated paraffin are optionally
incorporated.
Additives and Adhesive Aids
[0043] Also additives may be added to the inventive composition.
Suitable additives include thixotropic agents such as polyethers,
mildew-proofing agents, antibacterial agents, and adhesive aids,
for example, aminosilanes such as
.gamma.-aminopropyltriethoxysilane and
3-(2-aminoethylamino)propyltrimethoxysilane, and epoxysilanes such
as .gamma.-glycidoxypropyltrimethoxysilane and
.beta.-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.
[0044] The RTV heat conductive silicone rubber composition of the
invention may be obtained by intimately mixing the aforementioned
components (A) to (D) and optionally, curing catalysts, fillers and
additives in a dry atmosphere.
[0045] The RTV heat conductive silicone rubber composition of the
invention remains stable in the sealed state, but when exposed to
the air, it quickly cures by the airborne moisture. If necessary,
hydrocarbon solvents such as toluene and petroleum ether, ketones
or esters may be added to the composition as diluents, prior to
use.
[0046] The silicone rubber composition of the invention, provided
it is diluent-free, has a viscosity at 23.degree. C. of preferably
up to 300 Pas, more preferably 5 to 300 Pas, most preferably 10 to
200 Pas.
EXAMPLE
[0047] Examples of the invention are given below by way of
illustration and not by way of limitation. All parts are by weight.
The viscosity is a measurement at 23.degree. C.
Examples 1-3 & Comparative Examples 1-2
[0048] Component (A) used was a dimethylpolysiloxane capped with
hydroxyl groups at both ends of its molecular chain, having a
viscosity of 700 mPas (23.degree. C.). Component (B) used was a
dimethylpolysiloxane containing hydrolyzable groups, represented by
the structural formula below. ##STR6##
[0049] To components (A) and (B) were added 600 parts of spherical
aluminum oxide powder AS-30 having a mean particle size of 16 .mu.m
(trade name, Showa Denko K.K.) and 300 parts of aluminum oxide
powder AL-47-1 having a mean particle size of 1 .mu.m (trade name,
Showa Denko K.K.) as component (C). They were mixed at room
temperature for 20 minutes on a Shinagawa mixer. This mixture was
combined with 16 parts of phenyltri(isopropenyloxy)silane as
component (D), 0.8 part of
1,1,3,3-tetramethyl-2-[3-(trimethoxysilyl)propyl]guanidine-siloxane
as a curing catalyst, and 1 part of 3-aminopropyltriethoxysilane as
an adhesive aid in an anhydrous state. This was followed by
deaerating/mixing treatment for 20 minutes, obtaining a
composition. The amounts of components (A) and (B) used are shown
in Table 1.
[0050] The low-viscosity, heat conductive silicone rubber
compositions prepared as above were cured at 23.+-.2.degree. C. and
50.+-.5% RH for 7 days into sheets of 6 mm thick. They were
measured for hardness using a Durometer type A hardness meter.
[0051] Separately, the compositions were cured at 23.+-.2.degree.
C. and 50.+-.5% RH for 14 days into blocks of 12 mm thick, which
were measured for thermal conductivity using a thermal conductivity
meter Kemtherm QTM-D3 (quick thermal conductivity meter by Kyoto
Electronic Industry K.K.). To examine storage stability, 100 g of
each composition sample was contained in a glass bottle where it
was allowed to stand at 23.degree. C. for 1,000 hours. The sample
was rated NG when component (C) settled out and OK when no
settlement was observed.
[0052] The results are shown in Table 1. TABLE-US-00001 TABLE 1
Comparative Example Example 1 2 3 1 2 Components Component A 95 90
70 50 100 (pbw) Component B 5 10 30 50 0 Component C 900 900 900
900 900 Component D 16 16 16 16 16 Curing 0.8 0.8 0.8 0.8 0.8
catalyst Adhesive aid 1 1 1 1 1 Properties Viscosity 100 80 76 61
360 (Pa s) Hardness 90 90 87 82 90 (Durometer type A) Heat 2.5 2.4
2.4 2.5 2.4 conductivity (W/m K) Storage stability OK OK OK NG
OK
[0053] The results in Table 1 indicate that the addition of
component (B) enables a viscosity reduction, ensuring a composition
which is flowable and easy to work.
Examples 4-6 & Comparative Examples 3-4
[0054] Component (A) used was a dimethylpolysiloxane capped with
hydroxyl groups at both ends of its molecular chain, having a
viscosity of 700 mPas (23.degree. C.). Component (B) used was a
dimethylpolysiloxane containing hydrolyzable groups, represented by
the structural formula below. ##STR7##
[0055] To components (A) and (B) were added 600 parts of spherical
aluminum oxide powder AS-30 having a mean particle size of 16 .mu.m
(trade name, Showa Denko K.K.) and 300 parts of aluminum oxide
powder AL-47-1 having a mean particle size of 1 .mu.m (trade name,
Showa Denko K.K.) as component (C). They were mixed at room
temperature for 20 minutes on a Shinagawa mixer. This mixture was
combined with 16 parts of phenyltri(isopropenyloxy)silane as
component (D), 0.8 part of
1,1,3,3-tetramethyl-2-[3-(trimethoxysilyl)propyl]guanidine-siloxane
as a curing catalyst, and 1 part of 3-aminopropyltriethoxysilane as
an adhesive aid in an anhydrous state. This was followed by
deaerating/mixing treatment for 20 minutes, obtaining a
composition. The amounts of components (A) and (B) used are shown
in Table 2.
[0056] The low-viscosity, heat conductive silicone rubber
compositions prepared as above were cured at 23.+-.2.degree. C. and
50.+-.5% RH for 7 days into sheets of 6 mm thick, which were
measured for hardness using a Durometer type A hardness meter.
[0057] Separately, the compositions were cured at 23.+-.20.degree.
C. and 50.+-.5% RH for 14 days into blocks of 12 mm thick. They
were measured for thermal conductivity using a thermal conductivity
meter Kemtherm QTM-D3 (quick thermal conductivity meter by Kyoto
Electronic Industry K.K.). To examine storage stability, 100 g of
each composition sample was contained in a glass bottle where it
was allowed to stand at 23.degree. C. for 1,000 hours. The sample
was rated NG when component (C) settled out and OK when no
settlement was observed.
[0058] The results are shown in Table 2. TABLE-US-00002 TABLE 2
Comparative Example Example 4 5 6 3 4 Components Component A 95 90
70 50 100 (pbw) Component B 5 10 30 50 0 Component C 900 900 900
900 900 Component D 16 16 16 16 16 Curing 0.8 0.8 0.8 0.8 0.8
catalyst Adhesive aid 1 1 1 1 1 Properties Viscosity 140 130 98 80
360 (Pa s) Hardness 87 92 88 80 90 (Durometer type A) Heat 2.3 2.3
2.4 2.4 2.4 conductivity (W/m K) Storage stability OK OK OK NG
OK
[0059] The results in Table 2 indicate that the addition of
component (B) enables a viscosity reduction, ensuring a composition
which is flowable and easy to work.
Examples 7-9 & Comparative Examples 5-6
[0060] Component (A) used was a dimethylpolysiloxane capped with
trimethoxy groups at both ends of its molecular chain, having a
viscosity of 900 mPas (23.degree. C.). Component (B) used was a
dimethylpolysiloxane containing hydrolyzable groups, represented by
the structural formula below. ##STR8##
[0061] To components (A) and (B) were added 600 parts of spherical
aluminum oxide powder AS-30 having a mean particle size of 16 .mu.m
(trade name, Showa Denko K.K.) and 300 parts of aluminum oxide
powder AL-47-1 having a mean particle size of 1 .mu.m (trade name,
Showa Denko K.K.) as component (C). They were mixed at room
temperature for 20 minutes on a Shinagawa mixer. This mixture was
combined with 7 parts of methyltrimethoxysilane as component (D), 2
parts of titanium chelate catalyst Orgatix TC-750 (trade name,
Matsumoto Trading Co., Ltd.) as a curing catalyst, and 0.2 part of
3-aminopropyltriethoxysilane as an adhesive aid in an anhydrous
state. This was followed by deaerating/mixing treatment for 20
minutes, obtaining a composition. The amounts of components (A) and
(B) used are shown in Table 3.
[0062] The low-viscosity, heat conductive silicone rubber
compositions prepared as above were cured at 23.+-.2.degree. C. and
50.+-.5% RH for 7 days into sheets of 6 mm thick. They were
measured for hardness using a Durometer type A hardness meter.
[0063] Separately, the compositions were cured at 23.+-.2.degree.
C. and 50.+-.5% RH for 14 days into blocks of 12 mm thick, which
were measured for thermal conductivity using a thermal conductivity
meter Kemtherm QTM-D3 (quick thermal conductivity meter by Kyoto
Electronic Industry K.K.). To examine storage stability, 100 g of
each composition sample was contained in a glass bottle where it
was allowed to stand at 23.degree. C. for 1,000 hours. The sample
was rated NG when component (C) settled out and OK when no
settlement was observed.
[0064] The results are shown in Table 3. TABLE-US-00003 TABLE 3
Comparative Example Example 7 8 9 5 6 Components Component A 95 90
70 50 100 (pbw) Component B 5 10 30 50 0 Component C 900 900 900
900 900 Component D 7 7 7 7 7 Curing catalyst 2 2 2 2 2 Adhesive
aid 0.2 0.2 0.2 0.2 0.2 Properties Viscosity (Pa s) 130 110 92 80
460 Hardness 88 89 85 80 88 (Durometer type A) Heat conductivity
2.5 2.5 2.4 2.4 2.5 (W/m K) Storage stability OK OK OK NG OK
[0065] The results in Table 3 indicate that the addition of
component (B) enables a viscosity reduction, ensuring a composition
which is flowable and easy to work.
Comparative Example 7
[0066] 95 parts by weight of a dimethylpolysiloxane capped with
hydroxyl groups at both ends of its molecular chain, having a
viscosity of 700 mPas (23.degree. C.) and 5 parts by weight of a
dimethylpolysiloxane (viscosity at 25.degree. C.=12 Pas) endblocked
at one molecular chain terminal by silanol and endblocked at the
other terminal by trimethylsiloxy were used.
[0067] To the above dimethylpolysiloxanes were added 600 parts of
spherical aluminum oxide powder AS-30 having a mean particle size
of 16 .mu.m (trade name, Showa Denko K.K.) and 300 parts of
aluminum oxide powder AL-47-1 having a mean particle size of 1
.mu.m (trade name, Showa Denko K.K.). They were mixed at room
temperature for 20 minutes on a Shinagawa mixer. This mixture was
combined with 16 parts of phenyltri(isopropenyloxy)silane, 0.8 part
of
1,1,3,3-tetramethyl-2-[3-(trimethoxysilyl)propyl]guanidinesiloxane
as a curing catalyst, and 1 part of 3-aminopropyltriethoxysilane as
an adhesive aid in an anhydrous state. This was followed by
deaerating/mixing treatment for 20 minutes, obtaining a
composition.
[0068] The low-viscosity, heat conductive silicone rubber
composition prepared as above was cured at 23.+-.2.degree. C. and
50.+-.5% RH for 7 days into sheets of 6 mm thick. It was measured
for hardness using a Durometer type A hardness meter.
[0069] Separately, the composition was cured at 23.+-.2.degree. C.
and 50.+-.5% RH for 14 days into blocks of 12 mm thick, which was
measured for thermal conductivity using a thermal conductivity
meter Kemtherm QTM-D3 (quick thermal conductivity meter by Kyoto
Electronic Industry K.K.). To examine storage stability, 100 g of
the composition sample was contained in a glass bottle where it was
allowed to stand at 23.degree. C. for 1,000 hours. The sample was
rated NG when the heat conductive fillers settled out and OK when
no settlement was observed.
[0070] The results are shown in Table 4. TABLE-US-00004 TABLE 4
Comparative Example 7 Properties Viscosity (Pa s) 320 Hardness
(Durometer type A) 90 Heat conductivity (W/m k) 2.5 Storage
stability OK
[0071] The RTV heat conductive silicone rubber composition of the
invention eliminates the drawbacks of the prior art, imparts a high
stability even after a long-term storage, experiences a minimized
viscosity increase even when loaded with a large amount of heat
conductive filler, has good potting, coating and sealing
properties, and is suited for use in one package form.
[0072] Japanese Patent Application No. 2003-155286 is incorporated
herein by reference.
[0073] Although some preferred embodiments have been described,
many modifications and variations may be made thereto in light of
the above teachings. It is therefore to be understood that the
invention may be practiced otherwise than as specifically described
without departing from the scope of the appended claims.
* * * * *